Process for polymerizing high melt index olefins and polymerization catalysts used therefore

ABSTRACT

A process is disclosed for polymerizing an olefin to provide a polyolefin of high melt index which comprises contacting the olefin with a catalyst system obtained by heat activating a supported organophosphoryl chromium compound obtained by the reaction of chromium trioxide with an organophosphorous compound having the formula: ##STR1## wherein R is alkyl, aralkyl, aryl cycloalkyl, or hydrogen, but at least one R is other than hydrogen, and combining the heat activated supported material with a melt index increasing amount of at least one organoborane catalyst modifier having the formula: ##STR2## wherein m and n each is zero or 1, 
     R 1  and R 2  are each a hydrocarbyl group of from 1 to 10 carbon atoms, or one of R 1  and R 2  is hydrogen, or together R 1  and R 2  constitute a hydrocarbyl group of from 2 to 10 carbon atoms.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is related to the polymerization of olefins and,in particular, to a process and catalyst for producing very high meltindex polymers.

2. Description of the Prior Art

Peters, et al. in U.S. Pat. No. 2,892,826 describe the polymerization ofolefins in the presence of diborane, other hydrides of boron, or lowerboron alkyls adsorbed or absorbed on a group 5a oxide.

The use of chromium compounds in the polymerization of olefins is alsowell-known. U.S. Pat. Nos. 2,825,721 and 2,951,816 teach the use of CrO₃supported on an inorganic material such as silica, alumina orcombinations of silica and alumina, and activated by heating in reducingatmospheres, to polymerize olefins. When, however, a catalyst system ofthis type is used in techniques such as the well-known particle-formprocess, the resins produced, while useful in many applications, areunsatisfactory for other because of a deficiency in certain propertiessuch as melt index.

Attempts to improve the properties of polyolefins produced usingsupported, heat activated chromium oxide catalysts have been made byadding various compounds to the supported chromium oxide prior to theheat activation thereof. Thus, U.S. Pat. No. 3,484,428 discloses addingboranes or alkyl-substituted boranes to such a catalyst, and U.S. Pat.No. 3,780,011 refers to the use of alkyl esters of boron.

It is also known to utilize other chromium compounds as catalysts forthe polymerization of olefins. Such compounds include various silylchromate and poly-alicyclic chromate esters as described, for example,in U.S. Pat. Nos. 3,324,095; 3,325,101; 3,642,749; and, 3,704,287. Theuse of phosphorus-containing chromate esters in olefin polymerizationcatalysts have also been disclosed in the aforesaid U.S. Pat. No.3,704,287; and in U.S. Pat. Nos. 3,474,080 and 3,985,676. Other suchcatalysts are described in commonly assigned U.S. Pat. No. 4,100,104.Commonly assigned U.S. Pat. No. 4,118,340 of Rekers claims catalystscomprising reaction products of chromium trioxide and an organoboratecompound such as triethyl borate.

Certain of these catalytic materials may be employed in Ziegler-typecoordination catalyst systems, or in supported form, alone or inconjunction with metallic or orgnometallic reducing agents such as, forexample, trialkylaluminum compounds or alkylboranes. Catalyst systemsincorporating supported chromium compound catalysts and organometallicreducing agents, particularly organo-aluminum compounds, are disclosed,for example, in U.S. Pat. Nos. 3,324,101; 3,642,749; 3,704,287;3,806,500; 3,985,676; and in the aforesaid commonly assigned U.S. Pat.No. 4,100,104.

It has also been disclosed in U.S. Pat. Nos. 3,984,351 and 4,049,896,owned by the assignee of the present invention, that the properties ofolefin polymers, e.g., melt indices, may be substantially improved bythe use of a catalyst prepared by depositing chromium and aluminumcompounds on an inorganic support material and heat-activating thesupported composition in a non-reducing, preferably oxygen-containingatmosphere, at a temperature of from about 300° C. (572° F.) up to thedecomposition temperature of the support. The resulting material, aspreferably combined with a metallic and/or non-metallic reducing agent,e.g., a trialkylborane, provides a catalyst system capable of producingpolymers having improved flow properties and shear responses in additionto increased melt indices.

For example, U.S. Pat. No. 4,184,028 discloses a process forpolymerizing 1-olefins by contacting such olefin with a heat-activatedcatalyst system having deposited thereon a solid support material havingsurface hydroxyl groups, an organophosphoryl chromium reaction productof chromium trioxide and a phosphorous compound having the formula:##STR3## where R is alkyl, aralkyl, aryl, cycloalkyl or hydrogen, but atleast one R is other than hydrogen; and an aluminum compound. Inaccordance with commonly assigned copending application Ser. No. 931,598filed May 13, 1980, which has been allowed and is now U.S. Pat. No.4,252,926, the heat activated catalyst system of U.S. Pat. No. 4,184,028is combined with a hydrogenated alkylborane such as trimethylborane,tripropylborane, tributylborane, trihexylborane, tridodecylborane,tetraethyldiborane, and the like, prepared by reacting the alkyl boranein a solvent with hydrogen gas at a temperature range of 90° to 130° C.and at a pressure ranging from ambient to 1,000 p.s.i. Thepolymerization product formed by use of this catalyst system ischaracterized by, inter alia, elevated melt indices, better flowproperties and improved shear response.

SUMMARY OF THE INVENTION

In accordance with the present invention, it has been found that a veryhigh melt index polymer can be produced at acceptable productivity ratesby contacting at least one olefin with a catalyst system obtained byheat activating a supported organophosphoryl chromium compound andcombining the heat activated supported material with a solutioncomprising at least one organoboron compound represented by the generalformula: ##STR4## wherein m and n each is zero or 1 and R₁ and R₂ eachis a hydrocarbyl group of from 1 to 10 carbon atoms or R₁ and R₂together constitute a hydrocarbyl group of from 2 to 10 carbon atoms orone of R₁ and R₂ is hydrogen.

The chromium compound and, where present the aluminum compound, can bedeposited upon the support prior to heat activating as in the catalystpreparation procedures disclosed in U.S. Pat. Nos. 3,984,351; 3,985,676;and 4,049,896, and thereafter the organoborane compound can be added tothe activated material. Specifically, the heat activated supportedmaterial can be obtained by the reaction of chromium trioxide with anorganophosphorous compound having the formula: ##STR5## wherein R isalkyl, aralkyl, aryl, cycloalkyl, or hydrogen, but at least one R isother than hydrogen. The organoborane-containing solution may alsoinclude other boranes such as triethyl boron (TEB) or alkylaluminumcompounds such as triisobutylaluminum (TIBAL) or triethylaluminum (TEA).

The alkylborane or alkylaluminum compound is mixed together with theorganoborane compound prior to combining the latter with the supportedmaterial.

While slightly higher melt indices are generally associated with higherboron to chromium, B/Cr ratios, productivity rates do not similarlycorrespond. In aforesaid commonly assigned Ser. No. 931,598, now U.S.Pat. No. 4,252,926, an improvement in melt indexes was achieved with theuse of an alkylborane which had been pretreated with hydrogen atelevated temperatures and pressure. By use of the present invention,however, polymer melt indices have been increased by as much as 100% andgreater over the polymers produced by the process and catalyst disclosedin Ser. No. 931,598, now U.S. Pat. No. 4,252,926.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The inorganic support materials useful in the present invention includethose normally employed for supported chromium catalysts employed inolefin polymerizations, e.g., those described in U.S. Pat. No.2,825,721. Typically, these support materials are inorganic oxides ofsilica, alumina, silica-alumina mixtures, thoria, zirconia andcomparable oxides which are porous, have a medium surface area, and havesurface hydroxyl groups. Preferred support materials are silica xerogelsor xerogels containing silica as the major constituent. Especiallypreferred are the silica xerogels described in U.S. Pat. Nos. 3,652,214;3,652,215; 3,652,216; 3,978,002; and 4,053,565 each of which isincorporated by reference herein. These silica xerogels have a surfacearea in the range of from about 200 to about 500 m² /g and a pore volumegreater than about 2.0 cc/g, a major portion of which is provided bypores having pore diameters in the range of from about 300 to about 600A.

The chromium containing compounds useful in the present invention arethose disclosed in U.S. Pat. No. 3,985,676 and which comprise thereaction product of chromium trioxide with an organophosphorus compound.The organophosphosphorous compound and the chromium trioxide are broughttogether in a suitable inert solvent, e.g., cyclohexane, n-hexane,methylene chloride, carbon tetrachloride, etc. In this step in thepreparation of the catalyst system, the solid CrO₃ is slurried in thesolvent and the organophosphorus compound added. Over a period of time,e.g., about one hour, a reaction between the compounds ensues and thechromium trioxide disappears. During this period the solution becomesreddish-brown in color. It is ordinarily filtered simply to insure theabsence of any unreacted solid CrO₃. Among the organophosphoruscompounds which can be reacted with chromium trioxide to provide theorganophosphoryl chromium compounds herein are the triorganophosphatesand diorganophosphates including such compounds as triphenyl phosphate,tributyl phosphate, triethyl phosphate, trioctyl phosphate, trimethylphosphate, etc. Also suitable are the mono(-dihydrogen) phosphate orphosphite and di(hydrogen) phosphate derivatives (illustrativelyinclusive of monobutyl phosphate, dibutyl phosphate and monoethylphosphite) and these materials may of course comprise mixtures.Organophosphoryl chromium reaction products are also formed with suchphosphorus based compounds as phenyl phosphoric acid, diethyl ethylphosphonate and trioctyl phosphine oxide. Preferred organophosphoruscompounds can be represented by the formulas: ##STR6## where R is alkyl,aralkyl, aryl, cycloalkyl or hydrogen. The preferred organophosphorouscompounds are trialkyl phosphates such as triethyl phosphate.

Aluminum compounds which can optionally be employed in the presentinvention can be represented by the formula:

    Al(X).sub.a (Y).sub.b (Z).sub.c

wherein X is R, Y is OR, and Z is H or a halogen; a is 0-3, b is 0-3, cis 0-3, and a+b+c equals 3; and R is an alkyl or aryl group having fromone to eight carbon atoms.

Examples of such aluminum compounds include aluminum alkoxides such asaluminum sec-butoxide, ethylaluminum ethoxide, methylaluminum propoxide,diethylaluminum ethoxide, diisobutylaluminum ethoxide, etc.; alkyl orarylaluminum halides such as diethylaluminum chloride; arylaluminumcompounds such as triphenylaluminum, aryloxyaluminum compounds such asaluminum phenoxide and mixed aryl, alkyl and aryloxy, alkylaluminumcompounds.

The novel catalysts of the present invention can be prepared bydepositing the organophosphoryl chromium compound and, optionally, thealuminum compound, on the inorganic support in any suitable manner suchas by vapor coating or by impregnating the support with solutions of theorganophosphoryl chromium compound and the aluminum compound in asuitable inert solvent which is normally an anhydrous organic solvent.Such organic solvents include aliphatic, cycloalkyl and alarylhydrocarbons and their halogenated derivatives. A preferred organicsolvent is dichloromethane. The organophosphoryl chromium compound canbe applied to the support first or the aluminum compound can be appliedfirst or the chromium and aluminum compound can be applied together. Inthe usual method of catalyst preparation, the support is impregnatedfirst with the chromium containing compound and then the (optional)aluminum compound.

The most effective catalysts have been found to be those containing thechromium compound in an amount such that the amount of Cr by weightbased on the weight of the support is from about 0.25 to 2.5% andpreferably, from about 0.5 to 1.25%, although amounts outside of theseranges still yield operable catalysts. The aluminum compound should beadded in sufficient amounts to provide from about 0.1 to 10% of aluminumby weight based on the weight of the support and preferably from about0.5 to 5.5%, although other amounts outside of these ranges can be usedto prepare operable catalysts.

After the chromium-containing compound and the aluminum compound havebeen deposited on the inorganic support, the support is heated in anon-reducing atmosphere, preferably in an oxygen-containing atmosphere,at a temperature above about 300° C. up to the decomposition temperatureof the support. Typically, the supported compositions are heated at atemperature of from 500° to 1,000° C. The heating time may vary, forexample, depending on the temperature used, from 1/2 hour or less to 50hours or more. Normally, the heating is carried out over a period of 2to 12 hours. The non-reducing atmosphere which is preferably air orother oxygen-containing gas should be dry and preferably should bedehumidified down to a few parts per million (ppm) of water to obtainmaximum catalyst activity. Typically, air used in the proceduredescribed in this application is dried to less than 2-3 ppm of water.

The following organoboranes are preferred for use in the presentinvention: ##STR7## The selected organoborane is optionally combined insolution with another borane such as TEB, or with an alkylaluminumcompound such as triisobutylaluminum or triethylaluminum, and thereafterapplied to a heat treated supported organophosphoryl chromium compound,and optionally, an aluminum containing compound, as previouslydescribed. Combination of these components can be effected prior tofeeding the catalyst to an olfin polymerization reactor or thecomponents can be fed separately to the olefin polymerization reactorwith mixing taking place therein.

In proportioning the amount of organoborane compound (and alkylborane,if any) to the amount of chromium compound used in the catalyst systemsof the present invention, fairly wide latitude is available, but someguidelines have been established consistent with good yield, favorablepolymer properties and economic use of materials. For example, in theuse of catecholborane together with optional TEB, and an amount ofchromium compound sufficient to yield about 1% Cr by weight of hesupport, the parameters set forth below are representative. The atomicratios are based upon a calculation of the boron in the solution versusthe chromium content present in the chromium compound on the support.

Based upon a catalyst composition containing about 1% Cr based upon theweight of the support, the preferred total amount of borane-containingcompounds is that amount sufficient to yield a B/Cr atomic ratio ofabout 2.7/1. The preferred range of atomic ratios of B to Cr is fromabout 0.1/1 to about 10/1. The overall practicable limits, in terms of aB/Cr ratio, are from about 0.01/1 to about 20/1.

With respect to optional aluminum-containing components based upon acatalyst composition containing about 1% Cr by weight of the support,the preferred amount for use therewith, e.g., triisobutylaluminum, isabout 11.4% by weight and equivalent to an Al/Cr atomic ratio of about3/1. The preferred range of atomic ratios of Al to Cr is from about0.5/1 to about 8/1, or from about 1.9% to about 30% by weighttriisobutylaluminum. The overall practicable limits oftriisobutylaluminum in terms of the Al/Cr atomic ratio are from about0.1/1 to about 20/1, and in terms of weight are from about 0.4% to about75% by weight.

Identical considerations and procedures ae involved in the doubleactivation method of preparing the catalysts referred to above with theexception tht the aluminum compound is first deposited upon the supportand heat activated followed by deposition and activation of the chromiumcompound. Typically, the aluminum compound-coated support is heatedactivated at temperatures of from about 90° C. to about 1100° C.,preferably at from about 260° C. to about 820° C., and activation iscompleted by treating the chromium compound-coated support attemperatures within the range of from about 430° C. to about 1,100° C.,best results having been obtained by activation at temperatures of fromabout 850° C. to about 1,000° C.

As indicated above, the catalyst compositions of this invention aresuitable for use in conventional olefin polymerization andcopolymerization processes, in particular for 1-olefins having 2-8carbon atoms such as ethylene, propylene, butylene, and their mixtures,which are effected under temperature and pressure conditions generallyemployed in the art, e.g., temperatures of from about 40° C. to about200° C. and preferably from about 70° C. to 110° C., and pressures offrom 200 to 1,000 psig and preferably from 300 to 800 psig, as are usedin slurry or particle form procedures.

Hydrogen can be supplied to the reaction zone as a modifier, forexample, at a partial pressure of 30 to 120 psi, and is preferred foroptimization of results.

A series of olefin polymerizations, the results of which are givenbelow, were carried out to demonstrate the ability of the novel catalystsystems of the present invention to produce polymers having very highmelt indexes. The polymerizations were carried out in a stirredautoclave using isobutadiene as a diluent. The catalyst is added alongwith the isobutane solvent to a stirred one gallon autoclave. Thecontents of the stirred autoclave are then heated to the polymerizationtemperature, i.e., 88° to 108° C. Hydrogen, if used, is added and thenthe ethylene is added to give 10 mol % in the liquid phase at which timethe total pressure will be from about 425 to 455 psig. Polymerizationbegins almost immediately as noted by the ethylene coming from theethylene demand supply system to the reactor. After approximately onehour of polymerization, the reaction is terminated by dropping thereactor contents into a pressure let-down system. The melt index (M.I.)of the polymers prepared was determined using ASTM D-1238 (condition E).

The catalysts used in the polymerization runs were prepared inaccordance with the following catalyst preparation procedures:

CATALYST SYSTEM PREPARATION PROCEDURE

A. Polypor silica xerogel having a pore volume of about 2.5 cc/gprepared in accordance with U.S. Pat. No. 3,652,215 was added to a 2000ml, three-neck round bottom flask equipped with a stirrer, nitrogeninlet ahd y-tube with water condenser. A nitrogen atmosphere wasmaintained during the coating operation. Dichloromethane was then addedto the flask containing the silica gel and stirring was commenced toinsure uniform wetting of the gel. A dichloromethane solution of thereaction product of CrO₃ and triethyl phosphate prepared as described inU.S. Pat. No. 3,985,676 was then added to the flask in sufficientquantity to provide a dry coated catalyst containing about 1% by weightof Cr. The supernatant liquid was removed by filtration and the coatedgel was dried in a rotary evaporator at 60° C. and with 29 inches of Hgvacuum.

B. Dichloromethane was added to a similar flask as used in step A andwhile maintaining a nitrogen atmosphere stirring was commenced. To theflask was added the supported chromium composition prepared in step Aabove. A solution of dichloromethane and aluminum sec-butoxide wasprepared in a pressure equalizing dropping funnel and the funnelattached to the stirred flask. The aluminum sec-butoxide solution wasgradually added to the flask at the rate of 10 grams of solution perminute. After the addition of the solution was complete the slurry inthe flask was stirred for about 1 hour. The supernatant liquid wasremoved by filtration and the coated gel was dried in a rotaryevaporator at temperatures up to about 60° C. and 29 inches Hg vacuum.The amount of aluminum compound added depends on the % aluminum desiredfor the production of olefin polymers having specific propertiesnecessary for certain end use applications.

C. To heat activate the catalyst composition prepared in step B, thesupported catalyst was placed in a cylindrical container and fluidizedwith dry air at 0.20 feet per minute lineal velocity while being heatedto a temperature of 900° C. and held at this temperature for six hours.The activated supported catalyst was recovered as a powder.

D. Independent of the above procedure, a one ounce serum-capped bottlewas dried in an oven and purged with N₂. A 15% by weight solution of TEBin hexane was weighed out into the purged bottle. To this solution, aknown amount of catecholborane (liquid) was added using a needle andsyringe. Based on the weights of catecholborane and 15% TEB, the moleratios of catecholborane to TEB can be calculated. In Table I thesolutions of catecholborane/TEB used are listed with their weights andpercentages.

                  TABLE 1                                                         ______________________________________                                        Catecholborane/TEB Solutions                                                         gm     gm             %                                                Solution                                                                             15%    Catechol- %    Catechol-                                                                             Catecholborane                           No.    TEB    borane    TEB  borane  (mole)/TEB                               ______________________________________                                        1      6.95   1.15      12.8 14.2    0.90                                     2      45.0   4.72      13.6 9.5     0.57                                     3      15.2   1.1       14.0 6.8     0.40                                     4      19.1   0.82      14.4 4.1     0.23                                     5      17.2   0.37      14.7 2.1     0.12                                     ______________________________________                                    

The solutions prepared as indicated above were added to thepolymerization reactor with the supported catalyst component to form acatalyst system.

Table 2 shows the capability of the catecholborane/TEB system to formhigh melt index polymers at reactor conditions of 210° F. and 30 psi H₂.

                  TABLE 2                                                         ______________________________________                                        EFFECT OF CATECHOL BORANE/TEB                                                 CATALYST SYSTEM ON MELT INDEX OF                                              RESULTANT POLYMER                                                             Solution                                                                             Catechol-   Productivity                                               No.    borane/TEB  (g PE/g cat-hr)                                                                           MI   HLMI  MIR                                 ______________________________________                                        1      0.90        290         86   2408  27.7                                2      0.57        214         81   1860  22.7                                3      0.40        214         80   2090  26.0                                --     TEB         522         9.1  743   81.8                                       Reactor Conditions                                                            Temperature:                                                                           210° F.                                                       H.sub.2 :                                                                              30 psi                                                               Ethylene:                                                                              10 mole %                                                            B/Cr Ratio:                                                                            3/1, based on TEB                                                    Catalyst                                                                      Activation:                                                                            1650° F. for 6 hrs.                                    ______________________________________                                    

When catecholborane was present in the catalyst system, melt indices of80-86 were consistently obtained. These melt indices are considerablyhigher than the standard run using TEB alone. Furthermore, when usingthe catecholborane solutions, the polymer melt index ratios (MIR) weremuch lower than the standard TEB polymerizations indicating a narrowmolecular weight distribution (MWD).

Additional polymerizations were made using solutions havingcatecholborane/TEB mole ratios which were comparatively lower. Theresults of these runs in which the reactor temperature was 190° F. areshown in Table 3.

                  TABLE 3                                                         ______________________________________                                        EFFECT OF CATECHOLBORANE/TEB CATALYST                                         SYSTEM ON MELT INDEX OF RESULTANT POLYMER                                     Solu-                                                                         tion Catechol-  H.sub.3                                                                              Productivity                                           No.  borane/TEB (psi)  (g PE/g cat-hr)                                                                         MI   HLMI  MIR                               ______________________________________                                        4    0.23       30     210       16   1049  62.8                              4    0.23       120    141       63   2816  44                                5    0.12       30     297       14   1373  96                                5    0.12       120    264       55   2968  53                                --   TEB        30     547       1.3  209   155                               Reactor Conditions                                                            Temperature: 190° F.                                                   B/Cr Ratio:  3/1 based on TEB                                                 Ethylene:    10 mole %                                                        Catalyst                                                                      Activation:  Approximately 900° C. for 6 hrs.                          ______________________________________                                    

High melt indices were obtained even with the low ratios ofcatecholborane/TEB, and again lower MIR values were experiencedindicating narrower MWD with the use of the catecholborane solutions.

Combination additives for catalyst systems that produce high melt indexpolymers by use of the organoborane compounds described herein are notlimited to alkylboranes, but may also include alkylaluminum compoundssuch as triisobutylaluminum (TIBAL) and triethylaluminum (TEA).Accordingly, additional polymerization tests were made using the samesupported catalyst as described in steps A through C above, but withadditive solutions prepared with alkylaluminum compounds according tothe procedure set forth in step D.

                  TABLE 4                                                         ______________________________________                                        Catecholborane/TIBAL Solutions                                                Solu-         gm                 %      Catechol-                             tion gm 15%   Catecholborane                                                                            %      Catechol-                                                                            borane/                               No.  TIBAL    in solution TIBAL  borane TIBAL                                 ______________________________________                                        6    12.6     0.24        13.4   1.7    0.21                                  7    12.4     0.14        14.0   1.1    0.13                                  8    12.6     0.063       14.6   0.49   0.055                                 ______________________________________                                    

Table 4 shows the prepared solutions of catecholborane/TIBAL with theirweights and percentages. These solutions were introduced into thepolymerization reactor together with the supported catalyst component toform the catalyst system. Results of the polymerization runs at reactorcondition of 190° F. and the H₂ pressure at 30 psi are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                        EFFECT OF CATECHOLBORANE/TIBAL CATALYST                                       SYSTEM ON MELT INDEX OF RESULTANT POLYMER                                     Solution                                                                             Catechol-   Productivity                                               No.    borane/TIBAL                                                                              (g PE/g cat-hr)                                                                           MI   HLMI  MIR                                 ______________________________________                                        6      0.21        292         3.1  309   99                                  7      0.13        359         7.7  678   88                                  8      0.055       461         3.4  289   85                                  --     TIBAL       733         0.59  64   109                                 --     TEB         547         1.3  202   155                                 Reactor Conditions                                                            Temperature: 190° F.                                                   Al/Cr Ratio: about 3/1                                                        H.sub.2 :    30 psi                                                           Ethylene:    10 mole %                                                        Catalyst                                                                      Activation:  Approximately 900° C. for 6 hrs.                          ______________________________________                                    

Table 5 shows that even Catecholborane/TIBAL solutions having lowconcentrations of catecholborane result in a polymer with acomparatively high melt index than polymers produced using 15% TIBAL or15% TEB solutions in the catalyst system.

Catecholborane/TEA (triethylaluminum) solutions were prepared for use inthe catalyst system described herein in accordance with the value shownin Table 6.

                  TABLE 6                                                         ______________________________________                                        Catecholborane/TEA Solutions                                                                  gm            %                                               Solution                                                                             gm 25%   Catechol-                                                                              %    Catechol-                                                                             Catechol-                               No.    TEA      borane   TEA  borane  borane/TEA                              ______________________________________                                         9     11.1     0.055    24.3 0.48    0.019                                   10     14.0     0.081    24.2 0.56    0.022                                   11     10.7     0.161    22.9 13.8    0.057                                   ______________________________________                                    

Polymerization reactor conditions and resulting polymer properties areshown in Table 7. Noticeably, the melt indices of the resultant polymersincrease markedly as the Catecholborane/TEA ratio increases.

                  TABLE 7                                                         ______________________________________                                        Bench Scale Evaluation of                                                     Catecholborane/TEA Solutions as Modifiers                                     Solution                                                                             Catecholborane/                                                                            H.sub.2                                                                              Productivity                                       No.    TEA          (psi)  (g PE/g cat-hr)                                                                         MI   MIR                                 ______________________________________                                         9     0.019        30     610       1.2   108                                10     0.022        30     620       2.0  98                                                      120    628       28.8 59                                  11     0.057        30     527       6.3  86                                                      120    572       9.6  92                                  Reactor Conditions                                                            Temperature: 190° F.                                                   Al/Cr Ratio: about 3/1                                                        Ethylene:    10 mole %                                                        Catalyst                                                                      Activation:  approximately 900° C. for 6 hrs.                          ______________________________________                                    

While the mechanism responsible for the formation of such high meltindex polymers using the present system is not known, the use oforganoborane compounds of the type described herein results in polymershaving consistently higher melt indexes. In tests performed usingthexylborane solutions, polymer products having significantly increasedmelt indices were formed in polymerization reactions similar to the onesshown above. These results are shown in Table 8.

                  TABLE 8                                                         ______________________________________                                        Bench Scale Evaluation of                                                     Thexylborane Solutions as Modifier                                                       H.sub.2 Productivity                                               Boron Compound                                                                           (psi)   (g PE/g cat-hr)                                                                           MI   HLMI  MIR                                 ______________________________________                                        Thexylborane                                                                             30      501         2.4  360   150                                            120     382         12.3 1316  107                                 Thexylborane/                                                                            30      324         3.3  462   140                                 TEB.sup.(1)                                                                              120     318         2.1  269   128                                 TEB        30      364         0.60 102   170                                            120     286         1.14 170   149                                 Reactor Conditions                                                            Temperature: 190° F.                                                   Ethylene:    10 mole %                                                        Catalyst                                                                      Activation:  Approximately 900° C. for 6 hrs.                          ______________________________________                                         .sup.(1) Mixture of thexylborane/TEB at mole ratios of 1/1.              

The polymerization systems employing the thexylborane-containingcompounds produced polymers with a melt index nearly twice as much asthe TEB solution and in one case the melt index was ten times greaterfor the polymer produced by use of thexylborane.

While there have been described what are presently believed to be thepreferred embodiments of the invention, those skilled in the art willrealize that changes and modifications can be made thereto withoutdeparting from the spirit of the invention, and it is intended to claimall such changes and modifications as fall within the true scope of theinvention.

What is claimed is:
 1. A catalyst system obtained by heat activating asupported organophosphoryl chromium compound obtained by the reaction ofchromium trioxide with an organophosphorous compound having the formula:##STR8## wherein R is alkyl, aralkyl, aryl, cycloalkyl, or hydrogen, butat least one R is other than hydrogen, and combining the heat activatedsupported material with a melt index increasing amount of at least oneorganoborane catalyst modifier having the formula: ##STR9## wherein mand n each is zero or 1,R₁ and R₂ are each a hydrocarbyl group of from 1to 10 carbon atoms, or one of R₁ and R₂ is hydrogen, or together R₁ andR₂ constitute a hydrocarbyl group of from 2 to 10 carbon atoms.
 2. Thecatalyst system of claim 1 wherein the organoborane is selected from thegroup consisting of catecholborane, dimethoxyborane, ethoxyborane,thexylborane and disiamylborane.
 3. The catalyst system of claim 1wherein the catalyst is also prepared with an alkylborane compound. 4.The catalyst system of claim 3 wherein said alkylborane compound istriethylborane.
 5. The catalyst system of claim 1 wherein the catalystis also prepared with an alkylaluminum compound.
 6. The catalyst systemof claim 5 wherein the alkyl aluminum compound is triethylaluminum ortriisobutylaluminum.
 7. The catalyst system of claim 1 wherein thecatalyst system is supported upon silica gel or alumina.